新型改性聚己内酯型聚氨酯弹性体的合成及性能

doi:10.7503/cjcu20160528

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (12): 2291.doi: 10.7503/cjcu20160528

新型改性聚己内酯型聚氨酯弹性体的合成及性能

陈超, 包春燕(), 袁敏, 林秋宁, 朱麟勇()

华东理工大学精细化工研究所, 化学与分子工程学院, 上海 200237

收稿日期:2016-07-21 出版日期:2016-12-10 发布日期:2016-11-18
作者简介:联系人简介: 包春燕, 女, 博士, 教授, 主要从事智能生物材料研究. E-mail:baochunyan@ecust.edu.cn; 朱麟勇, 男, 博士, 教授, 主要从事生物可降解智能材料研究. E-mail:linyongzhu@ecust.edu.cn
基金资助:
国家自然科学基金(批准号: 21373084, 51273064)资助

Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers^†

CHEN Chao, BAO Chunyan^*(), YUAN Min, LIN Qiuning, ZHU Linyong^*()

Institute of Fine Chemical Engineering, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2016-07-21 Online:2016-12-10 Published:2016-11-18
Contact: BAO Chunyan,ZHU Linyong E-mail:baochunyan@ecust.edu.cn;linyongzhu@ecust.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21373084, 51273064)

摘要/Abstract

摘要：

用不同种类异氰酸酯[脂肪族六亚甲基二异氰酸酯(HDI)和脂环族异佛尔酮二异氰酸酯(IPDI)]对聚己内酯(PCL)进行改性, 得到两端为羟基的异氰酸酯改性的PCL预聚体. 将未改性和改性的PCL端羟基进行磷酸化后[磷酸化组分PCL210磷酸酯(A)、 PCL205/HDI磷酸酯(B)和PCL205/IPDI磷酸酯(C)]与双官能度的环氧(1,4-丁二醇二缩水甘油醚, E)进行开环交联反应, 得到生物相容且可降解的聚己内酯型聚氨酯弹性体材料(AE, BE和CE). 聚己内酯型聚氨酶弹性体的力学性能、静态水接触角、体外降解/溶胀和细胞毒性测试结果表明, PCL异氰酸酯的改性有助于提高材料的强度、弹性、耐疲劳性和降解速率, 同时未明显提高材料的细胞毒性.

关键词: 聚己内酯, 异氰酸酯改性, 聚氨酯弹性体, 生物可降解

Abstract:

Polycaprolactone(PCL) is a kind of excellent histocompatible and biodegradable materials due to the presence of amounts of esters that can be hydrolyzed by water or enzyme, which made PCL as one of Pure Food and Drug Administration(FDA) certified medical materials. However, the high crystallinity and poor hydrophility of polycaprolactone induce slow biodegradation rate, poor tenacity and fatigue durability although it has high mechanical strength. Therefore, modification on polycaprolactone was necessary. Herein, we used isocyanates[hexamethylene diisocyanate(HDI) and isophorone diisocyanate(IPDI)] to modify polycaprolactone and the phosphorylated prepolymers were reacted with bifunctional epoxy to form crosslinked and biodegradable elastomers. The test and analysis of mechanical properties, water contact angle, degradation/swelling and cell cytotoxicity in vitro indicated that the introduction of isocyanate helped to improve flexibility, fatigue resistance and degradation rate of the elastomers with no increased cytotoxicity.

Key words: Polycaprolactone, Isocyanate modification, Polyurethane elastomer, Biodegradable

TrendMD:

陈超, 包春燕, 袁敏, 林秋宁, 朱麟勇. 新型改性聚己内酯型聚氨酯弹性体的合成及性能. 高等学校化学学报, 2016, 37(12): 2291.

CHEN Chao, BAO Chunyan, YUAN Min, LIN Qiuning, ZHU Linyong. Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers^†. Chem. J. Chinese Universities, 2016, 37(12): 2291.

图/表 9

Scheme 1 Synthetic routes of PCL 210 phosphoester(A), PCL 205/HDI phosphoester(B), PCL205/IPDI phosphoester(C) and 1,4-butanediol diglycidy ether(E)

Scheme 2 Synthetic route of AE, BE and CE elastomers

Fig.1 1H NMR spectra of PCL 210 phosphoester(A), PCL 205/HDI phosphoester(B) and PCL205/IPDI phosphoester(C)

Fig.2 31P NMR spectra of PCL 210 phosphoester(a), PCL 205/HDI phosphoester(b) and PCL205/IPDI phosphoester(c)

Fig.3 1H NMR spectrum of 1,4-butanediol diglycidy ether

Fig.4 ATR-IR spectra of E(a), AE(b), BE(c) and CE(d) elastomers

Fig.5 Tensile(A) and compression(B) tests of AE(a), BE(b) and CE(c) elastomers

Fig.6 Stress-strain(A, C) and stress-time(B, D) curves of AE(A, B) and BE(C, D) systems

Fig.7 Mass-change curves(A) and cytotoxicity in vitro(B) of AE, BE and CE elastomers in PBS

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新型改性聚己内酯型聚氨酯弹性体的合成及性能

Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers^†

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新型改性聚己内酯型聚氨酯弹性体的合成及性能

Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers†

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Synthesis and Performance of Novel Modified Polycaprolactone Polyurethane Elastomers^†